d- and f- Block Chemistry (Basic Concepts In Chemistry)

188 Pages·2002·28.31 MB·English

by  Chris J. Jones

Cover images 0M urray Robertsonlvisual elements 1998-99, taken from the
109 Visual Elements Periodic Table
Copyright 0T he Royal Society of Chemistry 2002. All rights reserved.
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Preface
At first sight it may seem strange that metallic elements such as iron or
copper, which we encounter in machinery or electrical wiring, might also
be intimately involved in the function of living organisms. However, our
very survival depends upon the particular chemical properties of these
metallic elements, which belong to the d-block series known as the ‘transi-
tion metals’. To illustrate this point we might note that, after every breath
we take, the oxygen we inhale is collected by the red protein haemoglobin
present in our blood. The red color of blood arises from the presence of
iron in this protein, and it is to this iron that the oxygen becomes attached.
Through its attachment to hemoglobin, oxygen is transported in the
blood to sites in the body where another protein containing both iron and
copper effects its reduction. This releases energy as part of the process of
respiration. What is so special about iron and copper that biology has
selected them for these particular rbles? Why not nickel rather than iron?
What do we need to know about their chemistry to understand why they
are so specially suited to their particular functions?
Apart from their rather immediate importance in maintaining life,
transition elements are of major importance in enhancing the quality of
our daily lives. Among the materials we encounter each day, many either
contain transition elements or have been formed in processes which
involve them. Even plastic materials may have required the use of a tran-
sition metal catalyst in their manufxture.
In order to understand the biological rdes of transition metals, or
develop new chemical processes involving them, it is first necessary to
understand the principles which underly the chemistry of these elements.
In a short text such as this it is not possible to describe the chemistry of
the transition elements in any comprehensive way, and no attempt is
made to do so. Rather, it is the aim of this book to introduce some basic
principles which would allow a student of the subject to make more sense
iv Preface
of the varied, and sometimes surprising, chemistry they may encounter
when reading more comprehensive accounts of transition element chem-
istry. Several short primers already exist which provide an introduction to
the d- and f-block elements and it is not the aim of this text to duplicate
these, but rather to complement them.
The text is intended to take the reader through some of the topics cov-
ered in the first two years of an undergraduate course in chemistry. It
assumes some basic knowledge of topics which should be covered in oth-
er courses at this level. These include atomic structure, simple quantum
theory, simple thermodynamic relationships and electrode potentials. A
knowledge of group theory is not explicitly required to follow the text,
but reference is made to the symbols of group theory. The data in the text
are based on published sources. However, it should not be assumed that
data in the problems are based on actual measurements. Although report-
ed data have been used where possible, some values have been calculated
or invented for the purpose of the question.
As with all works of this type, the final text does not reflect the input of
the author alone. My thanks go to Matt Barton, Andy Millar and Steve
Vickers for checking a draft of the text, and to Martyn Berry for his help-
ful and insightful comments after reviewing the manuscript. However,
the responsibility for any errors which remain is mine alone, although
I assume no responsibility for the cover design which was beyond my
control!
Finally, my thanks must also go to my long-suffering wife, Judy, for her
forbearance and patience whilst my attentions have been redirected to yet
another ‘project’.
Chris J. Jones
Birmingham
till IOK-I\-CIlltl E X E C UT I V E EDI TO R S E D IJC AT I 0 N A L C 0 N S IJ LT A N T
Proffcssor E W Ahel Professor A G Davies Mr M Berry
Professor D Phillips
Projessor J D Woo1lin.c
This series of books consists of short, single-topic or modular texts, concentrating on the funda-
mental areas of chemistry taught in undergraduate science courses. Each book provides a
concise account of the basic principles underlying a given subject, embodying an independent-
learning philosophy and including worked examples. The one topic, one book approach ensures
that the series is adaptable to chemistry courses across a variety of institutions.
TITL1:S IN THE SEKIES
Stereochemistry D G Morris
Reactions and Characterization of Solids
S E Dunn
Main Group Chemistry W Iftvderson
d- and f-Block Chemistry C J Jones
Structure and Bonding J Burrett
Functional Group Chemistry J R Hunson

Contents
1.1 What are the Transition Elements? 1
1.2 Where do Transition Elements Come From? 4
1.3 The Historical Development of Transition Element Chemistry 7
1.4 Some Applications of the Transition Elements 14
2.1 Introduction 19
2.2 Transition Elements: Atomic Structure and Properties 20
3.1 Introduction 39
3.2 Binary Oxides, Fluorides and Chlorides 40
3.3 Thermodynamic Aspects of Compound Formation 44
4.1 Introduction 54
4.2 Coordination Compounds 55
4.3 Nomenclature 66
5.1 Introduction 72
5.2 The Thermodynamics of Complex Formation 73
5.3 Self-assembly and Metal Templated Reactions 90
vii
viii Contents
6.1 Introduction 97
6.2 The Crystal Field Model 98
6.3 The Molecular Orbital Model of Bonding 113
7.1 Introduction 130
7.2 The Electronic Spectra of Metal Complexes 131
7.3 The Magnetism of Transition Element Complexes 146